1. Field of the Invention
This invention is directed to halodihydrodioxins, their preparation and their polymers. The monomers of this invention provide amorphous homopolymers and copolymers that are resistant to ring opening side reactions during polymerization. The resulting polymers which are stable can be used for films and thermally stable molded objects, coatings with selected characteristics for substrates such as wood, glass, paper and metal and for protective packaging. This invention also concerns the preparation of polyhalogenated dioxoles.
2. Discussion of the Prior Art
P. L. Coe; P. Dodman; J. C. Tatlow; J. Fluor. Chem. 1975, 6, 115-128, describe the preparation of hexafluoro-p-dioxene in 18% yield by the dehydrofluorination of 2H-heptafluoro-p-dioxane under drastic conditions (fused potassium hydroxide at 150 degrees to 160 degrees). The authors also comment on the difficulty of dehydrofluorination of the --O--CFH-CF.sub.2 in some situations.
W. Schwertfeger; G. Siegemund; Angew. Chem. Int. Ed. Engl. 1980, 13, 126 disclose the preparation of fluorinated 1,4-dioxanes by the reaction of perfluorinated vicinal dicarbonyl compounds with ethylene dimesylate and potassium or cesium fluoride.
U.S. Pat. No. 4,343,742, by Muffler et al. claims a process for the manufacture of 2,3-perfluoro-1,4-dioxane.
U.S. Pat. No. 2,925,424 discloses cyclic fluoroketals of the formula: ##STR1## prepared by reacting fluoroketones with .beta.-haloethanol. R.sub.x and R.sub.y are perhalohydrocarbyl radicals of from 1 to 7 carbon atoms and R.sub.z is a divergent hydrocarbyl or halohydrocarbyl radical of 1 to 12 carbon atoms.
U.S. Pat. Nos. 3,865,845 and 3,978,030 disclose fluorinated dioxoles of the formula: ##STR2## where R.sup.1 and R.sup.2 are both perhalogenated hydrocarbyl radicals of 1 to 3 carbon atoms containing at least one F atom, and preparation of said dioxoles by reacting the corresponding dioxolanes with Mg. The dioxolanes are prepared by the fluorination with SbF.sub.3 --SbCl.sub.5 at 120.degree. C. of 2,2-bis-(perhaloalkyl)-4,4,5,5,-tetrachloro-1,3-dioxolanes, which in turn are prepared by chlorination of the dioxolanes described in U.S. Pat. No. 2,925,424 cited above.
U.S. Pat. No. 3,555,100 discloses the decarbonylation of fluorocarboxylic acid fluorides in the presence of SbF.sub.5.
U.S. Pat. No. 3,308,107 discloses perfluoro-2-methylene-4-methyl-l,3-dioxolane, its preparation from perfluoro-2,4-dimethyl-2-fluoroformyl-1,3-dioxolane and polymers thereof.
U.S. Pat. No. 3,532,725 discloses the photochlorination of alkyl and aralkyl ester groups of fluorinated esters in the presence of Cl.sub.2, UV radiation and optionally, CCl.sub.4 as solvent.
U.S. Pat. No. 3,557,165 discloses the conversion to acyl halides, in the presence of Lewis acids, of fluorinated esters wherein the ester groups contain polyhalogenated alkyl or aralkyl groups. The disclosed Lewis acids include FeCl.sub.3, SbCl.sub.5, ZnCl.sub.2, BF.sub.3, BCl.sub.3, MoCl.sub.5, tin chlorides and other metal chlorides, bromides and iodides.
U.S. Pat. No. 3,316,216 discloses the preparation of fluorinated dioxolanes of the formula: ##STR3## where R, R' and R" can include H, hydrocarbyl, haloalkyl and various other carbon-containing groups, and X and X' can include H, halogen and perfluoroalkyl, from fluoroketones and epoxides.
U.S. Pat. No. 3,324,144 discloses fluorodioxolanes of the formula: ##STR4## prepared from ketones and epoxides.
U.S. Pat. No. 3,749,791 discloses halogen-substituted 2,2 -bis(trifluoromethyl)-1,3-dioxolanes of the formula: ##STR5## where X is Cl or F and X' is H, Cl or F, and their preparation is by halogenation of 2,2-bis(trifluoromethyl-1,3-dioxolane.
U.S. Pat. No. 4,496,750 and U.S. Pat. No. 4,429,143 disclose the composition and a process for the preparation of halogenated dioxolanes of the formula: ##STR6## wherein: X.sub.1 is selected from the group consisting of Cl, F, COF, COCl, CO.sub.2 CCl.sub.3, CO.sub.2 R and CO.sub.2 M;
R is selected from the group consisting of H and alkyl of 1 to 4 carbon atoms; PA1 R.sub.F is perfluoroalkyl of 1 to 4 carbon atoms; PA1 M is selected from the group consisting of alkali metal ion and ammonium; PA1 X.sub.2, X.sub.3, X.sub.4 and X.sub.5, independently, are selected from the group, consisting of H, Cl and F; with the proviso that when PA1 X.sub.2, X.sub.3, X.sub.4 and X.sub.5 are each H, X.sub.1 is CO.sub.2 R or CO.sub.2 M. PA1 R.sub.F is a C.sub.1 to C.sub.8 linear or branched perfluoroalkyl with or without in-chain oxygen; PA1 X and Y together can be a perfluoroalkylene chain equal to (CF.sub.2).sub.n, where n=2-4.
M. Luedicke; W. Stumpf, Naturwiss 1953, 40, 363 describe the synthesis of heptachlorodioxane by chlorination of dioxane.